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21.
The basis set superposition error (BSSE) is often very important in the accurate calculation of dimerization energies. Accurate
prediction of thermochemical properties requires appropriate consideration of the basis set incompleteness error. Multilevel
methods introduce adjustable parameters to reproduce experimental data, that is, the higher level correction (HLC) in G3 and
adjustable coefficients in the MCCM. However, the HLC term is cancelled out and the adjustable coefficients in the MCCM do
not remove the BSSE completely. We have calculated the BSSE involved in the multilevel methods. The H2O and HF dimer systems were used as a test case. This study shows that empirical coefficients do reduce the BSSE in some cases
and an MCCM with good parameters can be used to reproduce dimerization energies within chemical accuracy without the BSSE
correction. 相似文献
22.
Co/Rh (Co:Rh = 2:2) heterobimetallic nanoparticles derived from Co(2)Rh(2)(CO)(12) react with alkynes and alpha,beta-unsaturated aldehydes such as acrolein, crotonaldehyde, and cinnamic aldehyde and release products resulting from [2 + 2 + 1]cycloaddition of alkyne, carbon monoxide, and alkene. alpha,beta-Unsaturated aldehydes act as a CO and alkene source. These reactions produce 2-substituted cyclopentenones. 相似文献
23.
Kwak WJ Han CK Chang HW Kim HP Kang SS Son KH 《Chemical & pharmaceutical bulletin》2003,51(3):333-335
A new triterpenoid saponin, loniceroside C was isolated from the aerial parts of Lonicera japonica. Its structure was established to be 3-O-beta-D-glucopyranosyl hederagenin 28-O-alpha-L-rhamnopyranosyl (1-->2)-[beta-D-xylopyranosyl(1-->6)]-beta-D-glucopyranosyl ester by spectroscopic techniques and chemical transformations. Loniceroside C showed in vivo antiinflammatory activity against mouse ear edema provoked by croton oil. 相似文献
24.
A novel process was developed to fabricate biodegradable polymer scaffolds for tissue engineering applications, without using organic solvents. Solvent residues in scaffolds fabricated by processes involving organic solvents may damage cells transplanted onto the scaffolds or tissue near the transplantation site. Poly(L-lactic acid) (PLLA) powder and NaCl particles in a mold were compressed and subsequently heated at 180 degrees C (near the PLLA melting temperature) for 3 min. The heat treatment caused the polymer particles to fuse and form a continuous matrix containing entrapped NaCl particles. After dissolving the NaCl salts, which served as a porogen, porous biodegradable PLLA scaffolds were formed. The scaffold porosity and pore size were controlled by adjusting the NaCl/PLLA weight ratio and the NaCl particle size. The characteristics of the scaffolds were compared to those of scaffolds fabricated using a conventional solvent casting/particulate leaching (SC/PL) process, in terms of pore structure, pore-size distribution, and mechanical properties. A scanning electron microscopic examination showed highly interconnected and open pore structures in the scaffolds fabricated using the thermal process, whereas the SC/PL process yielded scaffolds with less interconnected and closed pore structures. Mercury intrusion porosimetry revealed that the thermally produced scaffolds had a much more uniform distribution of pore sizes than the SC/PL process. The utility of the thermally produced scaffolds was demonstrated by engineering cartilaginous tissues in vivo. In summary, the thermal process developed in this study yields tissue-engineering scaffolds with more favorable characteristics, with respect to, freedom from organic solvents, pore structure, and size distribution than the SC/PL process. Moreover, the thermal process could also be used to fabricate scaffolds from polymers that are insoluble in organic solvents, such as poly(glycolic acid). Cartilage tissue regenerated from thermally produced PLLA scaffold. 相似文献
25.
Fluorescein has an extremely low luminescence intensity in acidic aqueous media. However, when it was bound to proteins, subsequent increase of luminescence intensity took place. Furthermore, when a hydrophobic tail, such as aliphatic hydrocarbons, was introduced to fluorescein, more dramatic increase of luminescence intensity was observed upon binding to proteins. In the present study, by utilizing this luminescence enhancement, three hydrophobic fluorescein dyes (5-dodecanoyl amino fluorescein, 5-hexadecanoyl amino fluorescein, and 5-octadecanoyl amino fluorescein) were examined as noncovalent fluorescent stains of protein bands in sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). Effective incorporation of the dyes to proteins in gels was accomplished either simply by adding dyes at the protein fixation step, or by treating gels with a staining solution after the fixation. The sensitivity of this staining method using the fluorescein derivatives was approximately 1 ng/band for most proteins. For some cases, protein bands containing as low as 0.1 ng were successfully visualized. In addition, the detection sensitivity showed much less protein-to-protein variation than silver staining. This new staining method was also successfully applied to two-dimensional electrophoresis of rat brain proteins. Its overall sensitivity was comparable to that of silver staining. 相似文献
26.
This paper describes an efficient synthetic route for various types of novel carbocyclic nucleosides. The required stereochemistry of the targeted nucleosides was successfully obtained with use of Grubbs cyclization and Trost allylic alkylation from the carbohydrate chiral template "D-lactose". 相似文献
27.
Zusammenfassung Die komplexe Koazervation im SystemG-A-H2O kann als zweistufiger Prozeß aufgefaßt werden. Das erste Stadium ist die Bildung des elektrisch neutralen Komplexes zwischen G und A unter Einfluß der elektrostatischen Anziehungskräfte. Die Stöchiometrie der gewonnenen Verbindung wird durch die Äquivalenz der Makroionen bestimmt.Nur elektrisch neutrale Komplexe können die neue Phase, d. h. das komplexe Koazervat bilden. Deshalb muß die Zusammensetzung der koazervaten Phase von pH abhängen und bei Veränderung des Verhältnisses der Polymere im Gemisch unveränderlich bleiben.Bei einem Verhältnis der Polymere, kleiner als das stöchiometrische, ist die Bildung geladener Komplexe möglich.Den Prozeß der komplexen Koazervation kann man mittels der Methode der Trübungsmessung bei Cs<6·10–3 g/100 g untersuchen. Hierbei ist die optische Dichte proportional der Menge des komplexen Koazervats oder des elektrisch neutralen Komplexes im System. 相似文献
28.
Reaction of 1,6-enynes with a hydrosilane in the presence of immobilized cobalt/rhodium bimetallic nanoparticles gives 2-methyl-1-silylmethylidene-2-cyclopentanes in the absence of carbon monoxide and 2-formylmethyl-1-silylmethylidene-2-cyclopentanes under 1 atm of carbon monoxide, respectively. [reaction: see text] 相似文献
29.
Using reaction rate data collected in aprotic solvents, we have determined that the Baylis-Hillman rate-determining step is second order in aldehyde and first order in DABCO and acrylate. On the basis of these data, we have proposed a new mechanism involving a hemiacetal intermediate. The proposed mechanism was then supported using two different kinetic isotope experiments. 相似文献
30.
A three-step one-pot synthesis of fenestranes from a readily available enyne and an alkyne diester has been carried out with cobalt nanoparticles and palladium(II) as catalysts. 相似文献